CN102887528B - Production technology of ammonium bifluoride - Google Patents
Production technology of ammonium bifluoride Download PDFInfo
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- CN102887528B CN102887528B CN201210389365.9A CN201210389365A CN102887528B CN 102887528 B CN102887528 B CN 102887528B CN 201210389365 A CN201210389365 A CN 201210389365A CN 102887528 B CN102887528 B CN 102887528B
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Abstract
The invention provides a production technology of ammonium bifluoride. The technology takes the byproduct fluosilicic acid of an anhydrous hydrogen fluoride production line and ammonia water as major raw materials and is used for producing ammonium bifluoride and co-product high-purity silicon dioxide. According to the technology, a silicon complex reagent is added to prevent generation of the complex precipitate of the ammonium fluosilicate and ammonium fluoride when in ammonia desilicication, and the separability of silicon dioxide from water is improved; and hydrofluoric acid is not used in the ammonium bifluoride production technology. The invention provides a new method for producing ammonium bifluoride by replacing the anhydrous hydrogen fluoride with the byproduct fluosilicic acid of a fluorine-source anhydrous hydrogen fluoride production line; and 6 fluorine atoms in fluosilicic acid are all released to replace hydrofluoric acid, thus the production cost of potassium fluoride can be greatly reduced, the product quality of potassium fluoride is improved, the raw material cost of ammonium bifluoride is lowered, and the benefits of ammonium bifluoride production enterprises are increased.
Description
Technical field
The invention belongs to chemical field, specifically a kind of production technique of ammonium bifluoride.
Background technology
Ammonium bifluoride purposes is quite extensive, and energy etching glass, is corrosive to skin.Can be used as chemical reagent, glass etching agent (participate in hydrofluoric acid with), fermentation industry sterilizing agent and sanitas, by the solvent of beryllium oxide metallic beryllium processed and the surface treatment agent of silicon steel sheet, also for the manufacture of pottery, magnesium alloy, the cleaning detergency of boiler feed water system and steam generation systems, and the acid treatment of oil field sandstone, also as alkylation, isomerization catalyst component.Be used for refining beryllium, welding electrode processed, cast steel, wood preservative etc.
Mostly the method for traditional mode of production ammonium bifluoride is to adopt the reaction of liquefied ammonia-hydrofluoric acid neutralisation to make, hydrofluoric acid in traditional technology is mainly made by fluorite and sulfuric acid reaction, traditional technology need to consume valuable resource fluorite, hydrofluoric acid cost is quite high, and fluorite and sulfuric acid reaction make the by-product fluosilicic acid that hydrofluoric acid produces and never have so effective that to have used, silicofluoric acid has 6 fluorine, and hydrofluoric acid only has a fluorine, therefore effectively use silicofluoric acid, make 6 fluorine in its silicofluoric acid all discharge, replace hydrofluoric acid, can greatly reduce the production cost of Potassium monofluoride.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of production technique of ammonium bifluoride.
Reaction formula of the present invention is:
H2SiF6+6NH4OH-----------6NH4F+SiO2+4H2O
2NH4F?-----------?NH4HF2?+NH3
This technique is with anhydrous hydrogen fluoride production line fluosilicic acid as byproduct, and ammoniacal liquor is the technique of main material production ammonium bifluoride and co-producing high-purity silicon-dioxide
The production technique of a kind of ammonium bifluoride of the present invention, is characterized in that comprising the steps:
1) silicofluoric acid is added to reactor, starts stirring, add silicon complexing agent, at the uniform velocity add ammoniacal liquor, fully reaction;
2) reaction solution is carried out to solid-liquid separation, solid is pulled an oar to clean and is obtained high-purity silicon dioxide, after being dried, obtains white carbon black;
3) reaction solution is added into transfer tank, precipitation 24h, clear liquid adds deamination still;
4) reaction solution is heated to deamination, the ammonia that reaction generates is absorbed as ammoniacal liquor through refrigeration cycle, is stored in basin, for desiliconization standby;
5) reaction solution is concentrated, the mother liquor after concentrating carries out crystallisation by cooling, centrifugation, and finished product is finished product ammonium bifluoride.
The production technique of described a kind of ammonium bifluoride, is characterized in that silicofluoric acid described in step 1) is anhydrous hydrogen fluoride production line by product, and its mass percentage concentration is 20-45%.
The production technique of described a kind of ammonium bifluoride, is characterized in that the amount of the silicon complexing agent that adds in step 1) is 0.2% of silicofluoric acid weight.
The production technique of described a kind of ammonium bifluoride, is characterized in that according to 1.1 times of the required mole number of reaction, adding ammoniacal liquor in step 1), and the mass percentage concentration that adds ammoniacal liquor is 25-29%.
The production technique of described a kind of ammonium bifluoride, it is characterized in that reacting in step 1) to the pH value of reaction end be 8.5-9.
The production technique of described a kind of ammonium bifluoride, is characterized in that in step 5), regulating pH value is 3.5-4.
The production technique of described a kind of ammonium bifluoride, is characterized in that the silicon complexing agent in step 1) is nitrilotriacetic acid(NTA) sodium.
The production technique of a kind of ammonium bifluoride of the present invention, add silicon complexometric reagent, while preventing with ammonia desiliconization, generate the complex compound sediment of ammonium silicofluoride and Neutral ammonium fluoride, improve the separation property of silicon-dioxide and water, in the technique of generation ammonium bifluoride, do not use hydrofluoric acid, provide a kind of new fluorine source anhydrous hydrogen fluoride production line fluosilicic acid as byproduct to replace anhydrous hydrogen fluoride to produce the method for ammonium bifluoride, make 6 fluorine in silicofluoric acid all discharge, replace hydrofluoric acid, can greatly reduce the production cost of Potassium monofluoride, to improve Potassium monofluoride quality product, reduce ammonium bifluoride material cost, promote ammonium bifluoride manufacturing enterprise benefit.
Embodiment
Embodiment 1
1, by anhydrous hydrogen fluoride production line by product mass percentage concentration, be that 20% silicofluoric acid adds reactor, start stirring, the nitrilotriacetic acid(NTA) sodium that adds 0.2% amount of silicofluoric acid weight, at the uniform velocity according to 1.1 times of the required mole number of reaction formula, to add mass percentage concentration be 25% ammoniacal liquor, fully reaction, the pH value of reaction end is 8.5-9.
2, after reacting completely in reactor, reaction solution carries out solid-liquid separation, and solid is pulled an oar to clean and is high-purity silicon dioxide, can do after drying white carbon black and sell.
3, reaction solution is added into transfer tank, precipitation 24h, clear liquid is squeezed into deamination still.
4, reaction solution is heated to deamination, the ammonia that reaction generates is absorbed as ammoniacal liquor through refrigeration cycle, is stored in basin, for desiliconization standby.
5, reaction solution concentrates, and adjusting pH value is 3.5-4, and the mother liquor after concentrating carries out crystallisation by cooling, centrifugation, and finished product is finished product ammonium bifluoride.
Embodiment 2
1, by anhydrous hydrogen fluoride production line by product mass percentage concentration, be that 30% silicofluoric acid adds reactor, start stirring, the nitrilotriacetic acid(NTA) sodium that adds 0.2% amount of silicofluoric acid weight, at the uniform velocity according to 1.1 times of the required mole number of reaction formula, to add mass percentage concentration be 25% ammoniacal liquor, fully reaction, the pH value of reaction end is 8.5-9.
2, after reacting completely in reactor, reaction solution carries out solid-liquid separation, and solid is pulled an oar to clean and is high-purity silicon dioxide, can do after drying white carbon black and sell.
3, reaction solution is added into transfer tank, precipitation 24h, clear liquid is squeezed into deamination still.
4, reaction solution is heated to deamination, the ammonia that reaction generates is absorbed as ammoniacal liquor through refrigeration cycle, is stored in basin, for desiliconization standby.
5, reaction solution concentrates, and adjusting pH value is 3.5-4, and the mother liquor after concentrating carries out crystallisation by cooling, centrifugation, and finished product is finished product ammonium bifluoride.
Embodiment 3
1, by anhydrous hydrogen fluoride production line by product mass percentage concentration, be that 40% silicofluoric acid adds reactor, start stirring, the nitrilotriacetic acid(NTA) sodium that adds 0.2% amount of silicofluoric acid weight, at the uniform velocity according to 1.1 times of the required mole number of reaction formula, to add mass percentage concentration be 25% ammoniacal liquor, fully reaction, the pH value of reaction end is 8.5-9.
2, after reacting completely in reactor, reaction solution carries out solid-liquid separation, and solid is pulled an oar to clean and is high-purity silicon dioxide, can do after drying white carbon black and sell.
3, reaction solution is added into transfer tank, precipitation 24h, clear liquid is squeezed into deamination still.
4, reaction solution is heated to deamination, the ammonia that reaction generates is absorbed as ammoniacal liquor through refrigeration cycle, is stored in basin, for desiliconization standby.
5, reaction solution concentrates, and adjusting pH value is 3.5-4, and the mother liquor after concentrating carries out crystallisation by cooling, centrifugation, and finished product is finished product ammonium bifluoride.
Table 1 is the ammonium bifluoride product quality analysis result (each embodiment respectively carries out twice experiment) of utilizing method of the present invention to produce, conformance with standard: HG/T 3586-1999.
The ammonium bifluoride product quality analysis result that table 1 utilizes method of the present invention to produce
Table 2 is high-purity silicon dioxide (rubber ingredients precipitated hydrated silica) mass analysis results (each embodiment respectively carries out twice experiment) of utilizing method of the present invention to produce, conformance with standard: HG/T 3061-2009.
High-purity silicon dioxide (rubber ingredients precipitated hydrated silica) the mass analysis result that table 2 utilizes method of the present invention to produce
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within being all included in protection scope of the present invention.
Claims (1)
1. a production technique for ammonium bifluoride, is characterized in that comprising the steps:
1) silicofluoric acid is added to reactor, start stirring, add silicofluoric acid weight 0.2% nitrilotriacetic acid(NTA) sodium as silicon complexing agent, at the uniform velocity according to reaction 1.1 times of required mole number, to add mass percentage concentration be 25% ammoniacal liquor, fully react to the pH value of reaction end be 8.5-9, described silicofluoric acid is anhydrous hydrogen fluoride production line by product, and its mass percentage concentration is 40%;
2) reaction solution is carried out to solid-liquid separation, solid is pulled an oar to clean and is obtained high-purity silicon dioxide, after being dried, obtains white carbon black;
3) reaction solution is added into transfer tank, precipitation 24h, clear liquid adds deamination still;
4) reaction solution is heated to deamination, the ammonia that reaction generates is absorbed as ammoniacal liquor through refrigeration cycle, is stored in basin, for desiliconization standby;
5) reaction solution is concentrated, regulating pH value is 3.5-4, and the mother liquor after concentrating carries out crystallisation by cooling, centrifugation, and finished product is finished product ammonium bifluoride.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210389365.9A CN102887528B (en) | 2012-10-15 | 2012-10-15 | Production technology of ammonium bifluoride |
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| CN201210389365.9A CN102887528B (en) | 2012-10-15 | 2012-10-15 | Production technology of ammonium bifluoride |
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| CN102887528A CN102887528A (en) | 2013-01-23 |
| CN102887528B true CN102887528B (en) | 2014-05-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445274A (en) * | 2014-11-28 | 2015-03-25 | 嵩县中科孵化器有限公司 | Preparation method of ammonium hydrogen fluoride |
| CN107934988B (en) * | 2017-12-14 | 2021-03-12 | 江西渠成氟化学有限公司 | Preparation method of ammonium bifluoride |
| CN109368660A (en) * | 2018-12-29 | 2019-02-22 | 贵州瓮福蓝天氟化工股份有限公司 | A kind of method of ammonium fluosilicate in reduction ammonium acid fluoride |
| CN111762797A (en) * | 2019-12-31 | 2020-10-13 | 承德莹科精细化工股份有限公司 | Production process for preparing low-silicon ammonium bifluoride by taking fluosilicic acid as raw material |
| CN111977671B (en) * | 2020-09-04 | 2021-08-27 | 包头市议源化工有限公司 | Method for preparing ammonium bifluoride by recycling rare earth fluorine-containing waste acid |
| CN113023749A (en) * | 2021-03-15 | 2021-06-25 | 盛隆资源再生（无锡）有限公司 | Method for resource utilization of etching process waste |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026997A (en) * | 1973-09-21 | 1977-05-31 | Bayer Aktiengesellschaft | Process for the production of ammonium fluoride from fluosilicic acid |
| US4915705A (en) * | 1986-08-01 | 1990-04-10 | Freeport Research And Engineering Co. | Production of silica and fluorine-containing coproducts from fluosilicic acid |
| CN101028931A (en) * | 2006-03-01 | 2007-09-05 | 多氟多化工股份有限公司 | Method for linked producing ammonium acid fluoride and white carbon black |
-
2012
- 2012-10-15 CN CN201210389365.9A patent/CN102887528B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026997A (en) * | 1973-09-21 | 1977-05-31 | Bayer Aktiengesellschaft | Process for the production of ammonium fluoride from fluosilicic acid |
| US4915705A (en) * | 1986-08-01 | 1990-04-10 | Freeport Research And Engineering Co. | Production of silica and fluorine-containing coproducts from fluosilicic acid |
| CN101028931A (en) * | 2006-03-01 | 2007-09-05 | 多氟多化工股份有限公司 | Method for linked producing ammonium acid fluoride and white carbon black |
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Application publication date: 20130123 Assignee: JIANGXI QUCHENG CHEMICAL Co.,Ltd. Assignor: Zhang Junhang Contract record no.: 2015360000067 Denomination of invention: Production technology of ammonium bifluoride Granted publication date: 20140507 License type: Exclusive License Record date: 20150603 |
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Effective date of registration: 20170118 Address after: 344800 Jiangxi city of Fuzhou province Jinxi County Industrial Park C District Patentee after: JIANGXI QUCHENG CHEMICAL Co.,Ltd. Address before: 322118 Jinhua City, Dongyang Province, Hengdian Town, Jing Jing community Jing Jing, No. 156 Patentee before: Zhang Junhang |
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